Adhesive in the form of sheets or the like



May 22, V1934. R, G. DREW ADHESIVE IN THE FORM oE SHEETS 0R THE LIKE Original Filed April ll, 1927 l! lllill!Illlllllllillllllllilllll lllllllllllllllllllllll appear or hereinafter be pointed out.

55. ful application of the paint brush when the lat- Patented May 22, 1934 s UNITED STATES THE Richard Gurley Drew, St.

Minnesota Mining St. Paul, Minn., a

ADHESIVE 1N THE FORM 0F LIKE s snEETs on Paul, Minn., 'assigner to & Manufacturing Company, corporation of Delaware Application August 27, 1931, serial No.

which is a continuation of original application Serial N0. 182,893, April 11, 1927.

this application Febru 710,030

Divided and ary 6, 1934, Serial No.

6 Claims. (Cl. S11-68)" My invention relates in general to adhesives,

. adhesive compositions or adhesive sheet or coatings, and more particularly to adhesive compositions or adhesive sheets or coatings, and still 5 more specifically to water soluble adhesives, ad-

hesive compositions or adhesive sheets or coatings and the method of producing the same.

While the invention has a broad field of usefulness, I have found it of peculiar utility for producing an adhesive coating for limiting the application of the spray of liquid finishing material, such as, for example, lacquers or painting operations in automobile body paint shops, and I therefore find it convenient to describe the invention in connection with such practice and product, it being understood, however, that such limited fields of specic description are employed p urely for purposes of illustration of an example of the utility of the invention in its several phases. beside such other novel fields of utility as-may In the work referred .to specifically above, my improved material may be used as an adhesive for holding protective paper aprons against surfaces on which it is not desired to apply the lacquer,.paint, paint spray or lacquer spray, such as, for example, glass windows, upholstery. rubber mats on running boards, bright metal parts, covering amd wrapping material in general, and the like.

My improved product may also be applied to a surface which in a subsequent step is to be nished by an application of a lacquer spray or painting or to a surface which has been iinished in order to prevent mingling of the colors, as for example, in two-color work.

My improved material may further be applied to paper or other suitable backing in the form'of sheeted material capable of being stored in piled sheets or in the laminationsas formed by rolling the sheets, ysuch as tape, or other such form as may beproper for the purpose contemplated. For certain preferred work, my improved material may be applied to paper to s impart minimum point contact yand inherent elasticity by applying the same to paper which isl toweled or crimped or otherwise '.shaped, to present a surface other, than flat and which has extensibility beyond that of the at paper web.

It is to' be observed that in nishingautomobile bodies with lacquers, paints vor the like of a plurality of colors, difficulty is found in limiting the application, owing to the division' ofthe spray where such is used, or requiringI skilter is used. In order to attain a clear and cleancut line of demarkatlon between several-colors, or within limited areas or applying a coating material within limited areas, masks in the form of adhesive vtapes have been' used. These are'6o of two general types, of which ythe zinc oxide tape and the rubber base tape form one group, i both ofk which use a cloth backing, and the ordinary gummed paper tape isan example of the other type. Both types of tape referred to present certain marked objections, amongst which may -be noted vthat the adhesive base thereon, such as the zinc oxide, is not water soluble and when removed a residue remains which has to be cleared away by some'expensive organic solvent. This is characteristic not only of zinc oxide but the rubber base adhesives. 'Ordinary gum base tape isenergized by wetting and. when applied to a surface, adheres so tenaciously that to remove the same requires soaking with water s for a long time and further necessitates scraping, tending to mar the underlying surface.

Furthermore, infthe case of the tapes referred to, when applied to apaint coated object, it frequently happens that'in separating the tape from the surface, patches o f the paint will be lifted from the surface and come away with the tape. Again, it frequently happens that these known tapes curl and become entangled in application ,85 and therefore becomel diiiicult, to manage and apply accurately. Similarly, if not correctly applied in the first instance, the retentive action of the surface to which the tape is applied immediately prevents removal, in this way not only marring the surface to which the tape is applied, but ruining the -same for reuse. Likewise, such tapes are often so energetic in their adhering action that the treated coat must be allowed toact and become formed before tape is applied thereto.

In the cases of covering certain materials, such as leather and glass, the known tapes are objectionable in that they will not readily adhere thereto or,if they are forced thereon by pressure, the time element required to -apply them and` thereafter clean or'remove the same by reason of the adhesive entering the pores of the former or becoming diffused thereover, as inthe case of the latter, adds to the cost of operation and detractsl from the result produced. It isfurthervknown that zinc oxide tape, rubber base tape or gummed paper tape tendf to deteriorate with the lapse of time, owing to the drying out of the material and oxidation thereof due to atmospheric exposure, no

with consequent loss of their power of adhering to the object to whichit is intended to be applied.

Y vWhile for simplicity in describing the invention andas an example of one method and means for making the same I have referred to glue, it is to be understood that I contemplate the employment of any adhesive lmaterial vsuitable for my purposes and that I employ the expression glue in the specification and claims in its broadest sense as an adhesive.

Among the objects of my present invention are the provision of an adhesive or coating material which is non-drying; 'the provision of an adhesive or coating material upon a base such as paper which may be applied to a lacquered, painted or varnished surface without injury thereof and whichis impermeable to freshly applied lacquer, paint or varnish; the provision of an adhesive or coating material upon a base such as paper, cloth or the like that may be applied to leather or other porous material without infiltration thereof and which is capable of removal therefroml without injury of the surface; the provision of a sheeted material including paper, cloth or the like having an adhesive coating thereon, which may be stored in piles or 'laminations without the use of slip sheeting; the provision of a sheeted material-including paper, cloth or the like which has an adhesive coating thereon and minimum point contact permitting ready removal thereof lby forming the same from creped material or toweled paper; the provision of a sheeted material having an adhesive coating thereon andN which is resilient, characterized by forming the same from creped 4or toweled paper; the provisionof a sheeted material having a paper or like base treated to render the same impermeable to coat.

ing materials suchas lacquers, paints, varnishes f' or the like; the provision of sheeted material havin a paper base, treated whereby the. same may dhesively applied to a surface and removedk without splitting of ,the paper; the provision of a sheeted material having a paper base treated vgher'ebyI an adhesive may be applied thereto withoutpermeating 'to thefother side thereof; the provision 'of a, sheettedl material having an uncalended paper basesaturated with an adhesive material whereby one'face thereof may be adhesively attached to'a surface and separated therefrom` without splitting ofthe paper, vthe provision of a sheeted material havinga bibulous, uncalendered paper base saturated with an adhesive whereby 'an adherent coating may be applied and the same used for adhesively attachingl the'same to a surface bythe application of pressure and to be separated from such surface without tearing orsplitting of the paperv or leaving a residuum of the adhesive surface.

The invention'still further has for an object lthereof the provision of a sheeted material impregnated with an adhesive material which is capable of being stacked or piled without the use of slip sheeting and'further resides in the provision of a process for treating an adhesive impregnated or saturated sheet whereby the sheet may be stacked or piled Without the use of slip sheeting and be separated without tearing of the adhesive coating or splitting of the paper base;

the provision of a process for rendering an adhesive impregnated sheet susceptible of stacking or piling without the use of slip sheeting including a glue base impregnated material and anl aldehydemodifying ingredient whereby, upon substantial'drying of the sheet, the surface will perlmit of stacking or piling .without adhesion, still glue while retaining adhesive properties, the "setting being accomplished in a partially dehydrated condition of the glue; the provision of a process for glue impregnating the paper and partially setting. the glue continuously without danger of breaking the web, characteristic of setting the glue in the wet condition; the provision of a process'for impregnating uncalendered, bibulous paper with glue and setting the glue in situ during the dehydrating of the impregnating glue solution.

My invention still further has for an object thereof the provision of a sheeted material having a base suchas paper, cloth or the like, including on one surface thereof a non-drying adhesive coatng comprising glue and a hygroscopic material, and which is capable of retaining the adhesive character under the most adverse atmospheric conditions, the sheet being characterized by freedom from loss of adhesiveness and setting-of the glue base, resulting from loss-of the hygroscopic agent due to absorption by the paper or cloth base and which may further be stacked or piled without the use of slip sheeting characterized by the absence of permeation of theadhesive coat to the back surface of the sheet.. l

The invention still further has for an object thereof the provision of a material having a paper base in which the filamentary material of the paper is locked and is resistant to tearing and splitting when in contact with an adhesive surface; the provision of a material having a paper base in which the filamentary material of the paper is locked and is resistant to tearing and splitting when in contact with an adhesive surface, characterized by surface treating and saturating the paper with `a glue or gelatine base material; the provision of a sheeted material having a paper base which is resistant to tearing and shock by forming the same from creped or toweled paper, and surface treating or saturating the same with -a glue or gelatine base; the provision of a sheeted material having a paper base surface treated or saturated with a glue or gelatine base material and further surface treated with a exibility iny ducing agent including glycerine whereby the To attain these objects. and such further' objects as may appear'herein or be hereinafter pointed out, I make reference to the accompanying drawing' forming a part hereof, in which Figure 1 is a perspective view illustrating my the use of intermediate slip v' `145 uity taken on a line 2 -2 of i like has attached thereto adjacent the edges 13 along its length a. strip of tape 10 by adhering the adhesive coating thereto with a portion 14 projecting beyond the edge 13, with ,the adhesive surfaces 11 exposed upon thegprojecting portion 14. The projecting portion '14 may thereafter be applied to fasten the mask or apron wherever desired, the adhesive face 11 included by this projecting portion serving as the means for attachment.

To prepare the tape 10'there is preferably rst provided a paper base which is preferably absorbent, approaching blotting paper, calendered or uncalendered. Preferably,` however this paper base is of the unsized, uncalendered variety and ispressed, molded or otherwise formed to have the appearance of toweled fabric, such as by crimping or creping the same.

The paper so provided is rst submitted to a preliminary treatment by a saturating solution involving a glue base. ofthe following materials in proportions. represent my preferred practice:-

. lPounds Dry glue 36A Water 72 Glue solution (approx. 16 Twaddell) 108 Complete swelling' is permitted, assisted by warming.

To this is then added-108 pounds of yellow glycerine.

Pounds 'The paper above described is preferably continuously submerged and passed through a bath of the saturating solution as above prepared and then passed through pressure rolls to squeeze off the excess and then dried by heating. It will be observed that ljustconiplete saturation is preferred as this step is closely related to the success or failure of the treatment. An insufficient saturation will be characterized by failure to completely bond the fibres of the unsized paper nor Will the saturating solution be present on the back side. An over-suiiicient saturation of the paper will render the surface unfit for subsequent coating, which will be observed as this description proceeds.

A paper so treated will-be found to have the bres thereof locked to materially strengthen the paper web and provide a highly flexible sheet. Where I use the toweled or creped variety of The saturating solution paper, this vsheet will be found -to be substantially elastic and resistant to tearing by shock, as where using the same for wrapping purposes.

Prior to the drying stepv above mentioned, in one form of the practice of my invention, after the paper has been saturated and passed through the pressure rolls, the web of material is subjected to a treatment tending'to insolubilize or tan the glue. 'Ihe insolubilizing or tanningv agents may be formaldehyde in solution or as a vapor, sodium carbonate solution of gallic and tannic acidsAphromium trioxide and chrome alum or other chrome and aluminum salts.

My preferred practice is to submerge the paper in a bath consisting of one part commercial formaldehyde and nine parts water by volume'. The lapse of time between saturating 4With glueglycerine water solution and formaldehyde does not seem to materially affect the quality of the paper. Formaldehyding on one side only, that is, the application of formaldehyde to one face of the-previously treated paper, is preferred for purposes which will hereinafter appear where it is desired to further coat' the untreated surface and leave the opposite surface substantially inactive.

The formaldehyding on one face only has the advantage that immediate insolubilizing or tanning may be practiced land further, treating `one y side only is less strain on a paper than complete submersion, particularly where the formaldehyde is in the form of a solution and the saturated paper before the excess Water is evaporated is of low tensile strength and therefore more subject to tear or break. The treated surface is then submitted to a neutralizing action and where formaldehyde is -used vfor-the insolubilizing or tanning action I may accomplish neutralization by subjecting the paper to a lime Water treatment.

y there is added to the saturating solution the tanning or vinsolubilizing agent. Where I use formaldehyde, I put an aldehyde compound into the glue solutionprior to the saturation step. It is preferred to retard the action of the aldehyde so that the insolubilizing or tanning of the glue is accomplished in the drying step. This retarding activity is accomplished by taking any aldehyde compound, such as formaldehyde, and adding ammonia thereto. In practice, equal molecular percentages of formaldehyde and ammonial are used in amounts equivalent to 5% of the aldehyde to the dry weight of the glue.

The saturating solution thus modified is used in the manner previously described. In the drying use a temperature between 100, to 120 C., which has been found to sufficiently set the glue with a speed of operation conducive to best practice.

The sheet so saturatedand heat treated will have the glue or gelatine base substantially insoluble and, in a sense, water-proof. The paper base will be particularly strengthened yand be resistant to sudden shock or stress. making it admirably suited for wrapping purposes. Particularly desirable elastic properties will be ob` tained where the paper base is of the toweled or Where I have described the use of dry glue with pale yellow glycerine, it will beobserved that good results have been obtainedtwith cheaper material such as low grade glue and using the crude rather than the pale yellow glycerine. Other'flexibility augmenting agents as a modifier forthe glue in.

place of the glycerine maybe used.' For certain purposes, rparticularly as will hereinafterrbe described', sulphonated oils suchk asTurkey red oil, sulphonated castor oil, may be used. These 'materials are not hygroscopic and tend to check, to

a certain extent, the tendency to absorb and carry too much Water. While I mayuse hygroscopic agents in general, for modifying the glue to retain a certain amount of water content inducing fiexibility, it is preferred to use organic `modifiers and for this purpose a sugar content fused in the glycerine of the saturating liquid has been found to be particularly desirable. A paper web saturated with the glue, formaldehyded or tanned as above described, has been found to be waterproof and particularly suitable as a'basefor forming the adhesive tape previously described when there is coated thereover the non-drying adhesive 1l. This non-drying adhesive may be of the glue-gelatine variety or the zinc oxide base or rubber base. Thus, I may use a water soluble coating or a water insoluble adhesive coating.

, The latter particularly serves to waterproof the glue base saturated fabric.

The waterproof coating may be deposited upon the glue saturated web by dipping this web ina solution vof asphaltum, removing the excess on the surface by means of pressure rolls. Although coating compositions such as paramn, bakelite, drying oils, such as linseed oil, and Varnishes may be used, asphaltum, because of its flexible qualities and low cost is preferred. This coating may be of the tacky variety. Where a bitumen base coating material is used, a'higher temperature resistant material may be obtained by blending gilsonite and viscolite, a bituminous product, and applying `them as a coating. The sheet so made with the waterproofing coating either of vthe adhesive variety or primarily of the waterproofing variety may be used as a waterproof-lng Wrapping paper capable of being stacked or piled without the use of -slip sheeting and is particularly tough, y

resilient and resistant to shock. v

Where I desire to form the tape l() with a nondrying adhesive 11 of the water soluble Variety,

the following coating compositionserving as an be sufficiently rapid. However, it is preferred to adhesive has been found particularly desirable in a manner which will be apparentas this description proceeds. The'composltion is as follows:

` Pounds Glue (dry) 250 Water 250 frlycerine 750 Granulatedsugar or of the dry glue weight 1871/2 This composition may be made by swelling the glue with a quantity of the specied water,

assisted by warming and thereafter the granulated.' sugar and glycerine are added with the remaining quantity of water. The glycerine is used for its flexiblity` augmenting and water retaining properties and the sugar is used not only because of its water retaining properties but because of its viscosity augmenting properties.

In general, it is preferred to use as such viscosity'augmenting and vwater rretaining agents, orgamc compositions. Of these there may be listedthe followingz- 1 (1) Sulphonated castor oil (2)- Honey (crude or refined) (3) Parainn and other waxes Gum chicle andv other vgums Crude glycerine L Smallpercentages of.l drying orfvnondrying o1 s 1 f (7) Venice turpentine f v(8) Shellac These organic ingredients-Iv have found particularly desirable in using with a glue saturated paper base as previously made in preference to inorganic hygroscopic materials. I have found that the inorganic `hygroscopic materials have a tendency to be absorbed by the paper base back ing tendingto set the adhesivecoating. In the claims where I use the term organic glue modifying agent I mean to include thereby such agents as above listed which, in certain cases, serve as substitutes for the sugar component.

In the present form of my adhesive, where I use sugar and glycerine as the glue modifying agents, the adhesive is prepared as follows: the quantity of glue is swelled in water, the action beingfacilitated by Warming. Separately, I fuse the sugar and glycerine content by mixing the same at a temperature of about 250 F. The temperature is preferably retained below 300 F. Temperatures in excess of 300 F. and up to 350 F. will produce an entirely different result. The water-glue mixture and the sugar-glycerine mixture lare then combined, preferably at the lower stated temperature. The material so prepared may be spread'upon any fabric webbing to obtain a vnon-drying adhesive coating. 'Ihis non-drying adhesive coating has been found to be particularly suitable by reason of its water soluble character. glue adhesive has been found tohave particu- 'A sugar-glycerine modified.v

larly desirable characteristics of water carrying duction `of an adhesive best suitedfor a non-- drying tape. Many` kinds aid grades of glue maybe used and still produce the desirable results, among which may be named the water soluble gums, such as trag'acanth and acacia.

Inferior glues or hide and bone glues have certain valuable characteristics, among which is the possibility of introducing solid materials without increasing the setting properties or `1ell strength of the adhesive. vThe working properties of the adhesive may thus be controlled by the proper selection of the solid material in accordance with the varying climatic and atmospheric conditions or the more particular tastes of the user to modify the aggressiveness of the adhesive to render the same more rapid in its action or retard the same.- These solid` materials may be magnesium carbonate, lead oxide, Whiting, zinc oxide andwhat may be termed paint pigments.

The adhesive as above made, particularly using the sugar-glycerine modifiers, may be spread` upon any webbing, cloth, paper or otherwise. It is preferred, however, to spread this adhesive uponthe glue saturated paper .previously described, particularly that which has had an insolubilizing or tanning treatment. The adhesive has been found to adhere to the glue saturated paper treated as above described particularly tenaciously and economy of this coating is affected by thenon-absorbent character of the previously saturated paper -for this adhesive. The

-adhesive coating makes tenacious contact when a saturated paper base is used. Where insoluvlgilized, tanned or formaldehyded glue saturated paper is used with the adhesive coating, sheets of this material may be stacked, piled or rolled and it has been found that the back surface of the. paper will not adhere to the underlying adhesive coating, avoiding the necessity of intermediatev slip sheeting. For certain purposes, the formaldehyding of the glue saturated paper may be avoided where stacking of the sheets or the storage of the same is to be in the form of a roll by thinly spreading glycerine uponI the adhesive v coating and the back thereof. These features are particularly desirable in that not only do they effect economy dueto saving of the cost of the slip sheeting but where the adhesive is made in the form of tape wound in rolls, standard lengths may be provided in rolls considerably reduced in size.

'The adhesive above described is preferably coated -upon the glue saturated and formaldehyde treated paper and is capable of stacking', piling or rolling without the use of slip sheeting.

1n general, it will be observed that I have provided an adhesive sheet or tape of the non-drying type which is susceptible-of use without the addition of modifying agents. The adhesive 'and the treated base lend themselves admirably suitable for painting, lacquering or spraying operations. They are impermeable and when applied on surfaces may be readily removed.

The specially treated paper and its adhesive 'coating duplicate results attainable heretofore only with cloth backing and, in addition, has marked advantages thereover. The paper base adhesive tape- (1) Produces-a flexible sheet with more body land density than cloth, particularly where a creped or toweled paper is used:

(2) High tensile strength is obtained by loading the paper with glue, particularly when acted upon by an insolubilizing, tanning or formaldehyding agent. This renders the glue .incapable of dissolving in water, which permits it to retain a considerable amount of its strength when in contact with water and hydroscopic materials which may constitute the adhesive film. When glycerine or.

other modifying elements are used, the saturated sheet is particularly `flexible and resistant to breaking thereofby bending;`

(3) The saturating and coating accomplish anl treatment of the paper, particularly when accom- `panied by insolubilizing, tanning or formaldehyding, also makes impossible any surface fibres breaking away or tearing away from `the backing and sticking to the adhesive `film when unwound from a roll. Thus, no modification of the adhesive film is effected.

l(5) The hygroscopic agent, such as glycerine,

retained in-'the saturated paper, maintains a water content in the paper backing of which it is a part; The adhesive film is therefore prevented from anchoring itself too securely to the reverse sideof the backing, that is, anon-drying adhesive -secures a hold or adheres toa dry surface much more thoroughly than to one which is moist or damp. Also, as the glue saturated paper has been insolubilized, tanned or formaldehyded,

the adhesive coating will not unite with the backing as thereis no solution possible 'between an untreated glue and an iiisolubilizedgelatine.

This application is a division of myapplication S. N. 559,740, filed August 27, 1931, which-'is a continuation of my application S. N. 182,893, filed April 11, 1927.

Having thus described my invention and illustrated its use, what I claim as new and desire t secure by Letters Patent, is

1. As a new article of manufacture, a sheeted material including a bibulous, uncalendered and unsized paper saturated with a composition comprising glue and a flexibilityv augmenting agent and a pressure sensitive adhesive coating of a' protein material on one surface thereof.

2. As a new article of manufacture, a sheeted material including a bibulous, uncalendered and unsized paper inpregnated with a composition .comprising glue and a flexibility augmenting agent, and a pressure sensitive adhesive coating of a glue on one'surface thereof.

3. As a new article of manufacture a sheeted material including a creped paper impregnated with a gelatine solution and an agent rendering the gelatine water resistant, and a pressure sensitive adhesive coating of a protein material on one surface thereof.

4. As a new article of manufacture, a sheeted material comprising a bibulous paper base impregnated without excess with a gelatinesolution including a flexibility augmenting agent, said sheet having the gelatine in one face thereof rendered water resistant, and a pressure sensitive adhesive coating of a glue on one surface thereof, the adhesive layer being on the opposite face to said Water resistant face.

5. As a new article of manufacture, a sheeted material comprising a bibulous paper base impregnated without excess with a gelatine soluand in direct contact with layers of said paper t base and water resistant face when said sheeted material is formed into rolls or stacks.

pregnated without excess with a gelatine vsolution including a flexibility augmenting agent, said 5 sheet having the gelatine in one face thereof rendered water resistant and a pressure sensitive adhesive coating of a giue attached to the sheet thus formedv andfpositioned .to be'interposed be-i f tween and in direct contact with the .layersvof said paper base land waterresistant tace when staid sheeted material is )formed into rolis'or s acks.

f GURLEY DREW. 

